Coating composition and articles made therefrom

ABSTRACT

The instant invention provides an aqueous dispersion, a coating composition, coating layers and coated article made therefrom. The coating composition according to the present invention comprises: (1) the inventive aqueous dispersion comprising the melt blending product of: (a) from 50 to 99 percent by weight of one or more first polyesters, based on the total solid content of the dispersion, wherein said one or more first polyesters have an acid number in the range of from less than 15, for example less than 10, or in the alternative less than 5, based on the total solid content of the one or more first polyesters; (b) from 1 to 50 percent by weight of one or more stabilizing agents comprising at least one second polyester, based on the total solid content of the dispersion, wherein said second polyester has a carboxylic acid group and an acid number equal to or greater than 15, for example greater than 20, based on the solid content of the second polyester; (c) one or more neutralizing agents; and (d) from 15 to 90 percent by weight of water, based on the total weight of the dispersion; wherein said dispersion has a solid content of 10 to 85 percent, based on the total weight of the dispersion; and (2) one or more cross-linking agents.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part application of theU.S. application Ser. No. 12/559,056, filed on Sep. 14, 2009, entitled“AQUEOUS DISPERSION, ITS PRODUCTION METHOD, AND ITS USE,” which is acontinuation application of the U.S. patent application Ser. No.10/925,693, filed on Aug. 25, 2004, and now U.S. Pat. No. 7,803,865 B2,which is entitled “AQUEOUS DISPERSION, ITS PRODUCTION METHOD, AND ITSUSE,” the teachings of which are incorporated by reference herein, as ifreproduced in full hereinbelow, which claims priority to the U.S.Provisional Application Ser. No. 60/497,527, filed on Aug. 25, 2003,entitled “FROTHS AND DURABLE FOAMS OF DISPERSED OLEFIN POLYMERS ANDARTICLES PREPARED FROM SAME,” and the U.S. Provisional Application Ser.No. 60/548,493, filed on Feb. 27, 2004, entitled “FROTH AND DURABLE FOAMOF DISPERSED OLEFIN POLYMERS, METHODS OF MAKING FOAM AND ARTICLESPREPARED FROM SAME,” the teachings of which are incorporated byreference herein, as if reproduced in full hereinbelow.

FIELD OF INVENTION

The instant invention relates to a coating composition and articles madetherefrom.

BACKGROUND OF THE INVENTION

The application of various treatment and pretreatment solutions tometals to retard or inhibit corrosion is well established. This isparticularly true in the area of metal food and beverage cans as well asnon-food metal containers. Coatings are applied to the interior of suchcontainers to prevent the contents from contacting the metal parts ofthe container. Contact between the metal and the food or beverage aswell as non-food substances can lead to corrosion of the metalcontainer, which can then contaminate the food or beverage or thenon-food contents of such metal containers. Corrosion is particularlyproblematic when food and beverage products are highly acidic natureand/or are having a high salt content such as a rhubarb-based productsor isotonic drinks. Also strong alkaline contents of non-food substancessuch as hair-dye may react with metal, for example, aluminum, parts ofcontainers. The coatings applied, for example, to the interior of foodand beverage cans also helps prevent corrosion in the head space of thecans, which is the area between the fill line of the food product andthe can lid. The coatings may be applied to the outside of metalcontainers to provide protection against the external environment or toprovide a decorative layer including fillers and/or pigments. Inaddition to corrosion protection, coatings for food and beverage cansshould be non-toxic and inert, and, if applied to the internal surface,should not adversely affect the taste or appearance, e.g. color, of thefood or beverage in the can or contribute to a contamination of thecontents of the can. Resistance to “popping”, “blushing” and/or“blistering” is also desired. Certain coatings are particularlyapplicable for application onto coiled metal stock, such as the coiledmetal stock from which the ends of cans are made, “can end stock” andvalve cups, e.g. top ends of aerosol cans. Since coatings designed foruse on can end stock are applied prior to the ends being cut and stampedout of the coiled metal stock, they are also typically flexible and/orextensible. For example, can end stock is typically coated on bothsides. Thereafter, the coated metal stock is punched and may be beadedor bent. It may also be scored for the “pop-top” opening and the pop-topring is then attached with a pin that is separately fabricated. The endis then attached to the can body by an edge rolling process.Accordingly, the coating applied to the can end stock typically has acertain degree of toughness and flexibility, such that it can withstandextensive fabrication processes, in addition to some or all of the otherdesirable features discussed above. Various coatings such as epoxy-basedand polyvinyl chloride-based, e.g. organosol type, coatings have beenused in the past to coat the interior of metal cans to preventcorrosion. However, there is a need for food and beverage can liners aswell as non-food container liners that provide improved properties suchas having resistance to degradation in corrosive media as well asappropriate level of flexibility.

SUMMARY OF THE INVENTION

The instant invention provides an aqueous dispersion, a coatingcomposition, coating layers and coated article made therefrom.

In one embodiment, the instant invention provides an aqueous dispersioncomprising the melt blending product of: (a) from 50 to 99 percent byweight of one or more first polyesters, based on the total solid contentof the dispersion, wherein said one or more first polyesters have anacid number in the range of from less than 15, for example less than 10,or in the alternative less than 5, based on the total solid content ofthe first polyester; (b) from 1 to 50 percent by weight of one or morestabilizing agents comprising at least one second polyester, based onthe total solid content of the dispersion, wherein said second polyesterhas a carboxylic acid group and an acid number greater than 15, forexample greater than 20, based on the solid content of the secondpolyester; (c) one or more neutralizing agents; and (d) from 15 to 90percent by weight of water, based on the total weight of the dispersion;wherein said dispersion has a solid content of 10 to 85 percent, basedon the total weight of the dispersion.

In an alternative embodiment, the instant invention further provides amethod for producing a aqueous dispersion comprising the steps of: (1)selecting one or more first polyesters having an acid number in therange of from less than 15, for example less than 10, or in thealternative less than 5, based on the total solid content of the firstpolyester; (2) selecting one or more stabilizing agents comprising atleast one second polyester having an acid number greater than 15, forexample greater than 20, based on the total solid content of the secondpolyester; (3) selecting one or more neutralizing agents; (4)melt-blending said one or more first polyesters, one or more stabilizingagents in the presence of water and one or more neutralizing agents; (4)thereby producing an aqueous dispersion having a solid content of 10 to85 percent, based on the total weight of the dispersion.

In another alternative embodiment, the instant invention furtherprovides a coating composition comprising: (a) the inventive aqueousdispersion, as described hereinabove; (b) one or more cross-linkingagents; (c) optionally one or more selected from the group consisting ofa polyolefin dispersion, acrylic latex, epoxy resin dispersion,polyurethane dispersion, alkyd dispersion, vinyl acetate dispersion, andethylene vinyl acetate dispersion.

In another alternative embodiment, the instant invention furtherprovides a coating layer comprising at least one or more film layersderived from the inventive coating composition, as describedhereinabove.

In another alternative embodiment, the instant invention furtherprovides a coated article comprising: (1) one or more substrates; (2) atleast one or more coating layers derived from the inventive coatingcomposition, as described hereinabove.

In another alternative embodiment, the instant invention furtherprovides a method for making a coated article comprising the steps of:(1) selecting a substrate; (2) selecting the inventive coatingcomposition, as described hereinabove; (3) applying said coatingcomposition to at least one surface of said substrate; (4) removing atleast a portion of the water from said the coating composition; (5)thereby forming one or more coating layers associated with saidsubstrate; and (6) thereby forming said coated substrate into a coatedarticle.

In another alternative embodiment, the instant invention furtherprovides a method for making a coated article comprising the steps of:(1) selecting a substrate; (2) forming said substrate into article; (3)selecting the coating composition, as described hereinabove; (4)applying said the coating composition to at least one surface of saidarticle; (5) removing at least a portion of the water from said thecoating composition; (6) thereby forming one or more coating layersassociated with at least one surface of said article; and (7) therebyforming said coated article.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the first polyester has a glass transitiontemperature (T_(g)) of at least 30° C.; for example at least 40° C.; orin the alternative, at least 50° C.; or in the alternative, at least 60°C.; or in the alternative, at least 70° C.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the substrate is a pre-coated substrate.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the substrate is metal, wood, paper, plastic,glass, leather, and/or concrete.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the dispersion and/or the coating compositionderived therefrom further comprises a catalyst.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the first polyester is a linear saturatedaromatic polyester with a glass transition temperature of greater than50° C. and an acid number of less than 5 mg KOH/g, and the secondpolyester is compatible with the first polyester, such that a dispersionwith a volume average particle size of less than 5 microns is produced.

In an alternative embodiment, the instant invention provides an aqueousdispersion, a coating composition, a coating layer, a coated article,method of producing the same, in accordance with any of the precedingembodiments, except that the aqueous dispersion and/or the coatingcompositions derived therefrom further comprise one or more bindercompositions such as acrylic latex, vinyl acrylic latex, styrene acryliclatex, vinyl acetate ethylene latex, polyurethane dispersion, alkyddispersion, epoxy dispersion, polyolefin dispersion, and combinationsthereof; optionally one or more fillers; optionally one or moreadditives such as catalysts, wetting agents, defoamers, flow agents,release agents, slip agents, anti-blocking agents, additives to masksulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters; optionally one or morelubricants such as fatty acid ester wax, silicon-based wax,fluorine-based wax, polyethylene or any other similar polyolefin wax,carnauba wax, lanolin wax or the like; optionally one or more corrosioninhibitors such as aluminum, and zinc: optionally one or more pigments,e.g. titanium dioxide, barium sulfate, mica, calcium carbonate, silica,zinc oxide, milled glass, aluminum trihydrate, talc, antimony trioxide,fly ash, and clay or the like; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, aromatic solvents and benzoate esters or thelike; optionally one or more dispersants, e.g. aminoalcohols, andpolycarboxylates; optionally one or more surfactants; optionally one ormore preservatives, e.g. biocides, mildewcides, fungicides, algaecides,and combinations thereof; optionally one or more thickeners, e.g.cellulosic based thickeners such as hydroxyethyl cellulose,hydrophobically modified alkali soluble emulsions (HASE thickeners suchas UCAR POLYPHOBE TR-116) and hydrophobically modified ethoxylatedurethane thickeners (HEUR); or optionally one or more additionalneutralizing agents, e.g. hydroxides, amines, ammonia, and carbonates;optionally one or more solvents or coalescing agents.

DETAILED DESCRIPTION OF THE INVENTION

The instant invention provides an aqueous dispersion, a coatingcomposition, coating layers and coated article made therefrom.

The coating composition according to the present invention comprises:(1) the inventive aqueous dispersion comprising the melt blendingproduct of: (a) from 50 to 99 percent by weight of one or more firstpolyesters, based on the total solid content of the dispersion, whereinsaid one or more first polyesters have an acid number in the range offrom less than 15, for example less than 10, or in the alternative lessthan 5, based on the total solid content of the first polyester; (b)from 1 to 50 percent by weight of one or more stabilizing agentscomprising at least one second polyester, based on the total solidcontent of the dispersion, wherein said second polyester has acarboxylic acid group and an acid number equal to or greater than 15,for example greater than 20, based on the solid content of the secondpolyester; (c) one or more neutralizing agents; and (d) from 15 to 90percent by weight of water, based on the total weight of the dispersion;wherein said dispersion has a solid content of 10 to 85 percent, basedon the total weight of the dispersion; and (2) one or more cross-linkingagents.

Aqueous Dispersion

The aqueous dispersion according to the present invention comprises themelt blending product of: (a) from 50 to 99 percent by weight of one ormore first polyesters, based on the total solid content of thedispersion, wherein said one or more first polyesters have an acidnumber in the range of from less than 15, for example less than 10, orin the alternative less than 5, based on the total solid content of thefirst polyester; (b) from 1 to 50 percent by weight of one or morestabilizing agents comprising at least one second polyester, based onthe total solid content of the dispersion, wherein said second polyesterhas a carboxylic acid group and an acid number equal to or greater than15, for example greater than 20, based on the solid content of thesecond polyester; (c) one or more neutralizing agents; and (d) from 15to 90 percent by weight of water, based on the total weight of thedispersion; wherein said dispersion has a solid content of 10 to 85percent, based on the total weight of the dispersion.

First Polyester

The aqueous dispersion comprises from 50 to 99 percent by weight of oneor more first polyesters based on the total weight of the solid contentof the aqueous dispersion. All individual values and subranges from 50to 99 weight percent are included herein and disclosed herein; forexample, the weight percent can be from a lower limit of 50, 55, 60, 65,or 70 weight percent to an upper limit of 60, 65, 70, 75, 80, 85, 90,95, or 99 weight percent. For example, the aqueous dispersion maycomprise from 55 to 95 percent by weight of one or more first polyester,based on the total weight of the solid content of the aqueousdispersion; or in the alternative, the aqueous dispersion may comprisefrom 60 to 90 percent by weight of one or more first polyester, based onthe total weight of the solid content of the aqueous dispersion; or inthe alternative, the aqueous dispersion may comprise from 65 to 90percent by weight of one or more first polyester, based on the totalweight of the solid content of the aqueous dispersion; or in thealternative, the aqueous dispersion may comprise from 75 to 95 percentby weight of one or more first polyester, based on the total weight ofthe solid content of the aqueous dispersion. The aqueous dispersioncomprises at least one or more first polyesters. The first polyester isa thermosetting polyester. Suitable thermosetting polyesters(hydrophobic polyester) for use in the present invention include, butare not limited to, hydroxyl functional polyesters with medium to highmolecular weight (>5000 g/mol Mw, preferably >10,000 g/mol M_(w), andmost preferably >20,000 g/mol M_(w)) polyester. Typically the hydroxylnumber of the thermosetting polyester will be at least 3 mg KOH/g (basedon resin solids) and preferably at least 5 mg KOH/g. The thermosettingpolyester will typically have an acid number of <15 mg KOH/g (based onresin solids), preferably <10 mg KOH/g, and most preferably <5 mg KOH/g.Preferred polyester thermosetting resins have a glass transitiontemperature (T_(g)) of at least about 30° C., preferably greater than50° C., and most preferably greater than 70° C.

The hydroxyl functional thermosetting polyester may be formed byconventional polycondensation techniques such as for example describedin Zeno W. Wicks, Jr, Frank N. Jones, S. Peter. Pappas, “OrganicCoatings, Science and Technology,” pp 246-257 (John Wiley & Sons, 1999,second edition) and references therein or in Houben-Weyl, “Methoden derOrganischen Chemie, Band E20, Makromolekulare Soffe, Polyester,” pp1405-1429. (Georg Thieme Verlag, Stuttgart 1987) and references therein.In one embodiment, a diol or polyol and a di-carboxylic acid orpolycarboxylic acid are charged into a conventional polymerizationvessel and reacted between about 150° C. and 280° C. for several hours.Optionally, an esterification catalyst may be used to decrease thereaction time. In general, to ensure the formation of a hydroxyl-groupterminated polyester, a small excess of diol may be used. It is alsounderstood that an esterifiable derivative of a polycarboxylic acid,such as a dimethyl ester or anhydride of a polycarboxylic acid, can beused to prepare the polyester.

In one embodiment of the invention, the thermosetting polyester is alinear saturated polyester. However, in some cases it might be desirableto introduce some branching points into the polyester. Triols or polyolsor polyacids can be used to provide branched polyesters.

Suitable and typical dicarboxylic acids or polycarboxylic acids, ortheir corresponding alkyl esters, that may be used to form thethermosetting polyester include saturated as well as unsaturateddicarboxylic acids such as, but not limited to, for example, isophthalicacid, maleic acid, maleic anhydride, malonic acid, fumaric acid,succinic acid, succinic anhydride, glutaric acid, adipic acid,2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid, dodecanedioicacids, phthalic acid, phthalic anhydride, 5-tert butyl isophthalic acid,tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalicanhydride, endomethylenetetrahydrophthalic anhydride, azelaic acid,sebacic acid, tetrachlorophthalic anhydride, chlorendic acid,isophthalic acid, trimellitic anhydride, terephthalic acid, naphthalenedicarboxylic acid, cyclohexane-dicarboxylic acid, dimer fatty acid, oranhydrides of any of these acids, or mixtures thereof.

Suitable diols and polyols that may be used to form the thermosettingpolyester include, but are not limited to, for example, ethylene glycol,diethylene glycol, triethylene glycol and higher polyethylene glycols,propylene glycol, dipropylene glycol, tripropylene glycol and higherpolypropylene glycols, 1,3-propanediol, 1,4-butanediol and otherbutanediols, 1,5-pentanediol and other pentane diols, hexanediols,decanediols, and dodecanediols, glycerol, trimethylolpropane,trimethylolethane, neopentyl glycol, pentaerythritol,cyclohexanedimethanol, dipentaerythtritol, 1,2-methyl-1,3-propanediol,1,4-benzyldimethanol, 2,4-dimethyl-2-ethylhexane-1,3-diol,isopropylidene bis(p-phenylene-oxypropanol-2),4,4′-dihydroxy-2,2′-diphenylpropane, 1,3-cyclohexanedimethanol,1,4-cyclohexanedimethanol (or mixtures of 1,3 and 1,4cyclohexanedimethanol, may be cis or trans), sorbitol, or mixturesthereof.

Suitable thermosetting polyesters are available, for example, fromEVONIK under the tradename DYNAPOL®.

In one embodiment, the hydroxyl functional, first polyester, may firstbe reacted with one or more multi-functional isocyanates such as, forexample, isophorone diisocyanate (IPDI), hexamethylene diisocyanate(HDI), dicyclohexylmethane-4,4′-diisocyanate (H12MDI), and 1,3 or1,4-bis(isocynatomethyl)cyclohexane, or mixtures thereof, to produce ahydroxyl-functional polyester-carbamate polymer.

In another embodiment, the hydroxyl functional, thermosetting polyestermay first be reacted with one or more partially blocked isocyanates orpolyisocyanates. In a preferred embodiment, the partially blockedisocyanate is a polyisocyanurate compound, such as a trimer, having atleast one free isocyanate group. More preferably, the blocked isocyanatehas at least two unblocked isocyanate groups. The blocked isocyanategroups of the at least partially blocked polyisocyanate can be anycombination of deblockable and/or non-deblockable isocyanate groups.Preferred blocking agents for forming deblockable isocyanate groupsinclude, but are not limited to ε-caprolactam, diisopropylamine (DIPA),methyl ethyl ketoxime (MEKO), and/or mixtures thereof. Preferredblocking agents for forming non-deblockable isocyanate groups include,but are not limited to, glycidol, hydroxyethyl acrylate, alcohols, andglycols. In one preferred embodiment, the deblockable isocyanate groupsdo not appreciably deblock at a temperature of less than 50° C., morepreferably the isocycanate groups do not appreciably deblock at atemperature of less than 100° C.

Stabilizing Agent Comprising a Second Polyester

The aqueous dispersion further comprises at least one or morestabilizing agents comprising one or more second polyesters to promotethe formation of a stable dispersion. The second polyester has acarboxylic acid group and an acid number equal to or greater than 15,for example greater than 20. The aqueous dispersion comprises 1 to 50percent by weight of one or more stabilizing agents, based on the totalweight of the solid content of the dispersion. All individual values andsubranges from 1 to 50 weight percent are included herein and disclosedherein; for example, the weight percent can be from a lower limit of 1,3, 5, 10 weight percent to an upper limit of 15, 25, 35, 45, or 50weight percent. For example, the dispersion may comprise from 1 to 25;or in the alternative, from 1 to 35; or in the alternative, from 1 to40; or in the alternative, from 1 to 45 percent by weight of one or morestabilizing agents, based on the total weight of the solid content ofthe dispersion.

The second polyester is a high acid, water dispersible, hydrophilicpolyester, which is used as the primary stabilizing agent for dispersingthe first polyester resin. The second polyester typically has an acidnumber in the range of from equal to or greater than 15 mg KOH/g (basedon resin solids), for example from 20 to 80 mg KOH/g (based on resinsolids). The carboxylic acid functionality of the second polyester iscritical to the present invention. In producing the waterbornedispersion, the acid functionality of the second polyester isneutralized with a suitable inorganic or organic base to providecolloidal stability. The high acid stabilizing polyester may also havehydroxyl functionality, but this is not required. Preferably the highacid stabilizing polyester has an OH number of at least 2 mg KOH/g(based on resin solids), preferably 5 mg KOH/g or greater, and mostpreferably 20 mg KOH/g or greater. The high acid stabilizing polyestermay be produced by conventional polycondensation techniques such as forexample described in Zeno W. Wicks, Jr, Frank N. Jones, S. Peter. Pappas“Organic Coatings, Science and Technology,” pp 246-257 (John Wiley &Sons, 1999, second edition) and references therein or in Houben-Weyl,“Methoden der Organischen Chemie, Band E20, Makromolekulare Soffe,Polyester” pp 1405-1429. (Georg Thieme Verlag, Stuttgart 1987) andreferences therein. In one embodiment, a diol or polyol and adi-carboxylic acid or polycarboxylic acid are charged into aconventional polymerization vessel and reacted between about 150° C. and280° C. for several hours. Optionally, an esterification catalyst may beused to decrease the reaction time. It may be preferable to use atwo-step process to provide a carboxyl functional polyester. In oneembodiment, an OH-functional polyester is first prepared so that thereis little, if any, free carboxylic acid and/or carboxylate functions,and which then in a subsequent step is reacted with a cyclicdicarboxylic anhydride, in a ring-opening and monoester-formingreaction, with free carboxylic acid and/or carboxylate groups then beingformed. The excess of OH functionality in the resin of the first step isdesigned in such a way that the final resin, after the reaction with thepolyacid functional molecules, will provide a carboxyl terminatedpolyester resin in which the acid number is typically in the range offrom equal to or greater than 15 mg KOH/g (based on resin solids), forexample from 20 to 80 mg KOH/g (based on resin solids).

The carboxylic acid component of the high acid stabilizing polyester maycontain one or more aliphatic, cycloaliphatic, araliphatic, and/oraromatic carboxylic acids with a COOH functionality of at least two, oranhydrides thereof. Suitable and typical dicarboxylic acids orpolycarboxylic acids, or their corresponding alkyl esters, that may beused to form the high acid stabilizing polyester include, but are notlimited to, saturated as well as unsaturated dicarboxylic acids such as,for example, but not limited to, maleic acid, maleic anhydride, malonicacid, fumaric acid, succinic acid, succinic anhydride, glutaric acid,adipic acid, 2-methyl-1,6-hexanoic acid, pimelic acid, suberic acid,dodecanedioic acids. phthalic acid, phthalic anhydride, 5-tert butylisophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid,hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride,azelaic acid, fumaric acid, sebacic acid, tetrachlorophthalic anhydride,chlorendic acid, isophthalic acid, trimellitic anhydride, terephthalicacid, naphthalene dicarboxylic acid, cyclohexane-dicarboxylic acid, andmixtures thereof.

The glycol component of the high acid stabilizing polyester may beethylene glycol, diethylene glycol, triethylene glycol and/or higherpolyethylene glycols, propylene glycol, dipropylene glycol, tripropyleneglycol and/or higher polypropylene glycols, 1,3-propanediol,1,4-butanediol and other butanediols, 1,5-pentanediol and/or otherpentane diols, hexanediols, decanediols, and/or dodecanediols, glycerol,trimethylolpropane, trimethylolethane, neopentyl glycol,pentaerythritol, cyclohexanedimethanol, a polyethylene or polypropyleneglycol having a molecular weight of about 500 or less,dipentaerythtritol, 1,3-butyleethylpropanediol,2-methyl-1,3-propanediol, 1,4-benzyldimethanol,2,4-dimethyl-2-ethylhexane-1,3-diol, isopropylidenebis(p-phenylene-oxypropanol-2), and mixtures thereof. In someembodiments, the aliphatic glycol may contain from 2 to 8 carbon atoms1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol (or mixtures of 1,3and 1,4 cyclohexanedimethanol, may be cis or trans),2,2,4,4-tetramethyl-1,3-cyclobutanediol (may be cis, trans, or a mixturethereof) 4,4′-dihydroxy-2,2′-diphenylpropane or mixtures thereof.

The composition of the high acid stabilizing polyester (secondpolyester) must be chosen so that it exhibits good compatibility withthe first polyester. If the compatibility is poor, a good water bornedispersion with small particle size (typically less than about 5 micronvolume average particle size diameter) and good stability may not beproduced. In addition, resulting coatings from such dispersions may havepoor appearance and may show reduced performance in coatings evaluationtests because of lack of compatibility. For example, if an aliphatic,high acid polyester (second polyester) is used to disperse an aromatic,hydrophobic first polyester, a poor dispersion will typically resultwith large particle size (typically greater than 5 micron volume averageparticle size diameter). One way to assess compatibility is to melt mixthe first polyester and the second polyester at a temperature abovetheir respective melting points. A blend with good compatibility willtypically result in a relatively clear or translucent blend, while anincompatible blend will typically result in an opaque or hazy, whitemelt blend. There may be other methods to determine compatibility suchas morphology determination by optical microscopy or transmissionelectron microscopy of the blend.

In selected embodiments, the stabilizing agent may optionally include asurfactant. Other stabilizing agents that may be used include, but arenot limited to, long chain fatty acids, fatty acid salts, or fatty acidalkyl esters having from 12 to 60 carbon atoms. In other embodiments,the long chain fatty acid or fatty acid salt may have from 12 to 40carbon atoms.

Additional stabilizing agents that may be useful in the practice of thepresent invention include, but are not limited to, cationic surfactants,anionic surfactants, or non-ionic surfactants. Examples of anionicsurfactants include, but are not limited to, sulfonates, carboxylates,and phosphates. Examples of cationic surfactants include, but are notlimited to, quaternary amines. Examples of non-ionic surfactantsinclude, but are not limited to, block copolymers containing ethyleneoxide and silicone surfactants. Stabilizing agents useful in thepractice of the present invention can be either external surfactants orinternal surfactants. External surfactants are surfactants that do notbecome chemically reacted into the base polymer during dispersionpreparation. Examples of external surfactants useful herein include, butare not limited to, salts of dodecyl benzene sulfonic acid and laurylsulfonic acid salt. Internal surfactants are surfactants that do becomechemically reacted into the base polymer during dispersion preparation.An example of an internal surfactant useful herein includes2,2-dimethylol propionic acid and its salts. Additional surfactants thatmay be useful in the practice of the present invention include cationicsurfactants, anionic surfactants, non-ionic surfactants, or combinationsthereof. Various commercially available surfactants may be used inembodiments disclosed herein, including: OP-100 (a sodium stearate),OPK-1000 (a potassium stearate), and OPK-181 (a potassium oleate), eachavailable from RTD Hallstar; UNICID 350, available from Baker Petrolite;DISPONIL FES 77-IS, DISPONIL TA-430, Disponil FES-32, and DiponilFES-993, each available from Cognis; RHODAPEX CO-436, SOPROPHOR 4D384,3D-33, and 796/P, RHODACAL BX-78 and LDS-22, RHODAFAC RE-610, andRM-710, and SUPRAGIL MNS/90, each available from Rhodia; and TRITONQS-15, TRITON W-30, DOWFAX 2A1, DOWFAX 3B2, DOWFAX 8390, DOWFAX C6L,TRITON X-200, TRITON XN-45S, TRITON H-55, TRITON GR-5M, TRITON BG-10,and TRITON CG-110, each available from The Dow Chemical Company,Midland, Mich., and ESPERSE grades E-100, E-506, E-328, E-355, andE-600, each available from Ethox Chemicals, LLC.

Additional stabilizing agents which could be used are solution orsuspension polymers consisting of ethylenically unsaturated monomerssuch as acrylic and/or methacrylic acid and their (C₁-C₃₀) esters oramides; acrylamide/methacrylamide and their N-substituted derivatives;acrylonitrile; styrene and substituted styrene derivatives.

Exemplary polymeric stabilizing agents include, but are not limited to,amphiphilic copolymer compositions, the copolymer comprising thereaction product of (i) from 5 to 95 wt. % of one or more hydrophilicmonomers and (ii) from 5 to 95 wt. % of one or more copolymerizableethylenically unsaturated hydrophobic monomers. These materials arewater soluble or emulsifiable, especially upon neutralization and canact as colloidal stabilizers. Exemplary stabilizing agents, for example,include, but are not limited to, butylacrylate and laurylmethacrylate.

Representative nonionic, water-soluble monomers suitable for productionof amphiphilic copolymer compositions, include, but are not limited to,acrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,N-vinylmethylacetamide, N-vinyl pyrrolidone, hydroxyethyl methacrylate,hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, t-butylacrylamide, N methylolacrylamide,alkyl(meth)acrylates such as methyl(meth)acrylate, butyl acrylate andethylacrylate, vinyl monomers such as ethylene, styrene, divinylbenzene,di-isobutylethylene, vinyl acetate and N-vinyl pyrrolidone, and allylmonomers such as allyl(meth)acrylate.

Representative cationic, water-soluble monomers suitable for productionof amphiphilic copolymer compositions include, but are not limited to,quaternary ammonium salts of amine functionalized monomers such asacrylamide, methacrylamide, N,N-dimethylacrylamide,N,N-diethylacrylamide, N-isopropylacrylamide, N-vinylformamide,N-vinylmethylacetamide, N-vinyl pyrrolidone, t-butylacrylamide,N-methylolacrylamide, tributylammonium ethyl(meth)acrylate TBAEMA,DMAEMA, DMAPMAM, diallyldimethylammonium chloride (DADMAC),methylacrylamidopropyltrimethylammonium chloride (MAPTAC),acrylamidopropyltrimethylammonium chloride (APTAC), N-vinyl pyrrolidone,vinylimidazole, polyquaternium-11 and polyquaternium-4.

“Anionic” or “acid-containing monomer” suitable for production ofamphiphilic copolymer compositions include, but are not limited to,ethylenically unsaturated monomers containing carboxylic acid,phosphonic acid, phosphinic acid, sulfinic acid and sulfonic acidgroups. Suitable examples include (meth)acrylic acid, maleic acid,succinic acid, itaconic acid, vinyl phosphonic acid and vinylsulfonicacid.

In an alternative embodiment, one or more stabilizing agents may bebased on resins such as polyester, epoxy resins, polyamide resins, whichmight be reacted with acrylic resins or acrylic monomers to formpolyester acrylate, polyamide acrylates epoxy resin acrylates.

Polyester acrylates as stabilizing agents may be formed via in-situpolymerization of copolymerizable ethylenically unsaturated monomers inpresence of polyesters. Examples include ethylenically unsaturated mono-or polyfunctional acids, ethylenically unsaturated mono- orpolyfunctional acid esters, amides, nitriles as well as vinyl monomersand vinyl ester with a polyester in or without presence of a reactionfluid. Polyester acrylates in solvents can be dried according tosuitable methods known to those of ordinary skill in the art.

Suitable epoxy resins for producing stabilizing agents may be obtainedin accordance with conventional procedures well known to those ofordinary skill in the art by reacting a polyepoxide with a suitablepolynucleophile. Suitable epoxides include, but are not limited to,glycidyl ethers, and other epoxy group containing molecules. Suitablepolynucleophiles include, but are not limited to, polyhydric phenols,and poly phenols, polythiols, aliphatic polyalcohols or polybasic acidsor polyamines. Exemplary suitable epoxies, for example, include, but arenot limited to, glycidyl ether that contains at least two glycidyl ethergroups per polyglycidyl ether molecule (e.g. an at least diglycidylether) with a polyhydric phenol that contains at least two hydroxylgroups in the polyhydric polyphenol (e.g., at least dihydric phenol or adiphenol) in presence of a conventional catalyst at an elevatedtemperature with or without solvent present. Another class of epoxyresins may be obtained in accordance with conventional procedures wellknown to those of ordinary skill in the art by reacting, for example, apolyglycidyl ether that contains at least two glycidyl ether groups perpolyglycidyl ether molecule (e.g. an at least diglycidyl ether) with apolybasic acid that contains at least two carboxyl groups per polybasicacid molecule (e.g. an at least dibasic polycarboxylic acid) in presenceof a conventional catalyst at an elevated temperature with or withoutsolvent present.

Epoxy acrylates for producing stabilizing agents may be formed viain-situ polymerization of copolymerizable ethylenically unsaturatedmonomers in presence of epoxy resins. Examples include, but are notlimited to, ethylenically unsaturated mono- or polyfunctional acids,ethylenically unsaturated mono- or polyfunctional acid esters, amides,nitriles as well as vinyl monomers and vinyl ester with an epoxy resinsin or without presence of a reaction fluid. Alternatively a polymericacid functional acrylic resin can be reacted with an epoxy resin in thepresence of a suitable catalyst to form epoxy acrylate. Epoxy acrylatesin solvents can be dried according to suitable methods known to those ofordinary skill in the art. In one embodiment an acid functionalizedpolyester may be used, wherein the epoxy is reacted, for example, withan excess of an acid functional polyester.

Neutralizing Agent

The stabilizing agent may be partially or fully neutralized with aneutralizing agent. In certain embodiments, neutralization of thestabilizing agent, the second polyester, may be from 50 to 250 percenton a molar basis; or in the alternative, it may be from 50 to 200percent on a molar basis; or in the alternative, it may be from 50 to150 percent on a molar basis; or in the alternative, it may be from 50to 120 percent on a molar basis. For example, the neutralizing agent maybe a base, such as ammonium hydroxide, sodium hydroxide, or potassiumhydroxide. Other neutralizing agents can include lithium hydroxide, forexample. In another alternative, the neutralizing agent may, forexample, be a carbonate. In another alternative, the neutralizing agentmay, for example, be any amine such as monoethanolamine, or2-amino-2-methyl-1-propanol (AMP). Amines useful in embodimentsdisclosed herein may include diethanolamine, triethanolamine, and TRISAMINO™ (each available from Angus), NEUTROL™ TE (available from BASF),as well as triisopropanolamine, diisopropanolamine, andN,N-dimethylethanolamine (each available from The Dow Chemical Company,Midland, Mich.). Other useful amines may include ammonia,monomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, mono-n-propylamine, butylamine,dibutylamine, tributylamine, dimethyl benzyl amine, dimethyln-propylamine, N-methanol amine, N-aminoethylethanolamine,N-methyldiethanolamine, monoisopropanolamine, N,N-dimethylpropanolamine, 2-amino-2-methyl-1-propanol, 1,2-diaminopropane,tris(hydroxymethyl)-aminomethane, ethylenediamineN,N,N′N′-tetrakis(2-hydroxylpropyl)ethylenediamine, N,N,N′,N′tetramethylpropanediamine, 3-methoxypropyl amine, imino bis-propyl amineand the like. In some embodiments, mixtures of amines or mixtures ofamines and other surfactants may be used. In one embodiment, theneutralizing agent may be a polymeric amine, e.g. diethylene triamine.Those having ordinary skill in the art will appreciate that theselection of an appropriate neutralizing agent depends on the specificcomposition formulated, and that such a choice is within the knowledgeof those of ordinary skill in the art. In one embodiment, amines withboiling points below 250° C. may be used as the neutralizing agents.

Fluid Medium

The aqueous dispersion further comprises a fluid medium. The fluidmedium may be any medium; for example, the fluid medium may be water.The aqueous dispersion comprises from 15 to 90 percent by weight ofwater, based on the weight of the dispersion; for example, thedispersion comprises from 20 to 85 percent by weight of water, based onthe weight of the dispersion; or in the alternative from 30 to 75percent by weight of water, based on the weight of the dispersion; or inthe alternative from 40 to 75 percent by weight of water, based on theweight of the dispersion; or in the alternative from 40 to 65 percent byweight of water, based on the weight of the dispersion. Water content ofthe dispersion may preferably be controlled so that the solids content(one or more first polyesters plus stabilizing agent comprising a secondpolyester) is in the range of from 10 to 85 percent by weight, based onthe weight of the dispersion. For example, the dispersion comprises from20 to 70 percent by weight of solid contents (one or more firstpolyesters plus stabilizing agent comprising a second polyester), basedon the weight of the dispersion; or in the alternative, from 25 to 70percent by weight of solid contents (one or more first polyesters plusstabilizing agent comprising a second polyester), based on the weight ofthe dispersion; or in the alternative, from 35 to 70 percent by weightof solid contents (one or more first polyesters plus stabilizing agentcomprising a second polyester), based on the weight of the dispersion;or in the alternative, from 35 to 65 percent by weight of solid contents(one or more first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 40 to 70 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 40 to 65 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 45 to 65 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion; or in thealternative, from 50 to 70 percent by weight of solid contents (one ormore first polyesters plus stabilizing agent comprising a secondpolyester), based on the weight of the dispersion.

The fluid medium may optionally contain one or more suitable solvents.For example the one or more optional solvents include but are notlimited to, e.g. glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediolmonoisobutyrate, alcohols, ketones, glycol ether esters, mineralspirits, aromatic solvents and/or esters or the like; optionally one ormore dispersants, e.g. aminoalcohols, and/or polycarboxylates.

Additional Components

The aqueous dispersion of the present invention may optionally beblended with one or more binder compositions such as acrylic latex,vinyl acrylic latex, styrene acrylic latex, vinyl acetate ethylenelatex, epoxy dispersion, polyurethane dispersion, alkyd dispersion,polyolefin dispersion, and combinations thereof; optionally one or morefillers; optionally one or more additives such as catalysts, wettingagents, defoamers, flow agents, release agents, slip agents,anti-blocking agents, additives to mask sulfur staining, pigmentwetting/dispersion agents, anti-settling agents, UV stabilizers,adhesion promoters; optionally one or more lubricants such as fatty acidester wax, silicon-based wax, fluorine-based wax, polyethylene or anyother similar polyolefin wax, carnauba wax, lanolin wax or the like;optionally one or more corrosion inhibitors such as aluminum, and zinc:optionally one or more pigments, e.g. titanium dioxide, barium sulfate,mica, calcium carbonate, silica, zinc oxide, milled glass, aluminumtrihydrate, talc, antimony trioxide, fly ash, and clay or the like;optionally one or more co-solvents, e.g. glycols, glycol ether,2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, alcohols, mineralspirits, aromatic solvents and benzoate esters or the like; optionallyone or more dispersants, e.g. aminoalcohols, and polycarboxylates;optionally one or more surfactants; optionally one or morepreservatives, e.g. biocides, mildewcides, fungicides, algaecides, andcombinations thereof; optionally one or more thickeners, e.g. cellulosicbased thickeners such as hydroxyethyl cellulose, hydrophobicallymodified alkali soluble emulsions (HASE thickeners such as UCARPOLYPHOBE TR-116) and hydrophobically modified ethoxylated urethanethickeners (HEUR); or optionally one or more additional neutralizingagents, e.g. hydroxides, amines, ammonia, and carbonates; optionally oneor more solvents or coalescing agents.

In addition, the aqueous dispersion may be blended with one or moredispersions, emulsions, suspensions, colloidal suspensions, and thelike. For example the aqueous dispersion of the invention may be blendedwith polyurethane dispersion, alkyd dispersion, epoxy dispersion, vinylacetate emulsion, acrylic emulsion, polyolefin dispersion, vinyl acetateethylene emulsion, and/or the like. The addition of the additionalcomponents, as described herein, may be achieved as part of the processfor making the dispersion, i.e. the additional components are addedwhile producing the aqueous dispersion; or in the alternative, theadditional components may added post aqueous dispersion production, i.e.the additional components are added into the aqueous dispersion afterthe dispersion is produced; or in the alternative, combinations thereof,i.e. additional components may be added during the process for makingthe dispersion and additionally such additional components are addedpost dispersion production as well.

Crosslinking Agent

The aqueous dispersion may optionally further comprise at least one ormore crosslinking agents to promote crosslinking and or one or morecatalyst to increase the rate of crosslinking. Such catalysts aregenerally known, and the selection of suitable catalyst typicallydepends on the selection of the crosslinking agent and other factorssuch as conditions for such crosslinking. Such catalysts include, butare not limited to, depending on type of crosslinker—strong acids, weakacids or compounds containing metals, such as dodecyl benzene sulfonicacid, p-toluene sulfonic acid, di-nonylnaphtalene disulfonic acid,methane sulfonic acid, phosphoric acid or weak acids such as ammonium orphosphonium salts or tin, bismuth, zirconium or aluminum chelatecompounds. Exemplary catalysts include, but are not limited to, NACURE™,K-Kure™ and K-Kat™, available from King Industries, CYCAT™ from CytecIndustries, and/or FASCAT™ from Arkema Inc. The aqueous dispersion ofthe instant invention comprises 0.5 to 50 percent by weight of one ormore crosslinking agents, based on the total weight of the solid contentof the dispersion. All individual values and subranges from 0.5 to 50weight percent are included herein and disclosed herein; for example,the weight percent can be from a lower limit of 0.5, 1, 3, 5, 10. 15, or20 weight percent to an upper limit of 10, 12, 15, 18, 20, 25, 30, 35,40, 45, or 50 weight percent. For example, the dispersion may comprisefrom 1 to 18; or in the alternative, from 1 to 15; or in thealternative, from 1 to 12; or in the alternative, from 1 to 10; or inthe alternative, from 1 to 20; or in the alternative, from 1 to 30; orin the alternative, from 1 to 40; or in the alternative, from 1 to 45;or in the alternative, from 1 to 50 percent by weight of one or morecrosslinking agents, based on the total weight of the solid content ofthe dispersion. In selected embodiments the crosslinking agent may, forexample, be phenol-formaldehyde resins, amino-formaldehyde resinsincluding, but not limited, to urea-formaldehyde resins, melamineformaldehyde resins, benzoguanamine formaldehyde resins, anhydrideresins, epoxy group containing resins such as epoxy resins, epoxy groupcontaining polyester or acrylic resins and blocked or un-blockedisocyanate resins, and combinations of two or more thereof, providedthat the combinations of such crosslinkers is compatible.

Crosslinking agent may be a compound, which reacts with a reactivefunctional group contained in the dispersion formulation; therebyfacilitating their crosslinking. Such functional groups can be presentin both the first polyester as well as the stabilizing agent comprisinga second polyester.

For example, reactive functional groups include, but are not limited to,acid groups such as carboxylic acid groups, free or in the neutralizedform, or any functional groups having another active hydrogen by anothercomponent such as alcohol groups, amino groups, epoxy groups, or thelike.

Crosslinkable functional groups in the cross-linking agent are groupscapable of reacting with the reactive functional group of the firstpolyester or the stabilizing agent comprising a second polyester. Forexample, a carbodiimide group, an oxazoline group, an isocyanate group,an epoxy group, a methylol group, an aldehyde group, an acid anhydridegroup, a hydroxy group, an aziridinyl group or a silane group can beused in a crosslinker.

Another possibility of crosslinking acid functional groups is by use ofmultivalent metal ions by reaction of the aforementioned acid groupswith a multivalent metal ion containing substance, such as zinc oxide.

Carboxylic acids could also be crosslinked in reactions withmultifunctional olefinic unsaturated substances under catalysis of astrong acid. Multifunctional carbonates could also react with carboxylicacids to give ester linkages with liberation of carbon dioxide.

In the alternative, crosslinking may be accomplished via free radicalcrosslinking, initiated by addition of peroxides or via radiation, e.g.,electron beam.

With respect to crosslinkable functional groups, one or more may bepresent in a crosslinking agent. In the alternative, two or morecrosslinkable functional groups may be present in a single molecule.

The cross-linking agent having the above described crosslinkablefunctional group may be a waterdispersed or waterdispersible orwater-soluble substance. In one embodiment, exemplary crosslinkingagents include, but are not limited to, an aqueous monomeric orpolymeric substance, which contains two or more oxazoline groups,carbodiimide groups, epoxy groups, isocyanate groups, methylol groupsetc. or several of these per molecule.

An exemplary oxazoline crosslinking agent is an aqueous polymer havingtwo or more oxazoline groups in its molecules, substances can beobtained by polymerizing an oxazoline group-containing monomer and, asrequired, an ethylenic unsaturated monomer. Alternatively an oxazolinecrosslinking agent can also be obtained by reaction between a nitrilegroup and an aminoethanol group, dehydration of a hydroxylalkylamidegroup and the like.

Crosslinking agents having two or more carbodiimide groups can beproduced from diisocyanate compounds by a condensation reactionaccompanied by decarboxylation reaction of a diisocyanate compound.Examples of the diisocyanate compound include, but are not limited to,1,5-naphthylene diisocyanate, 4,4′-diphenylmethane diisocyanate,4,4′-diphenyldimethylmethane diisocyanate, 1,4-phenylene diisocyanate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexanemethylenediisocyanate, cyclohexane-1,4-diisocyanate, xylylene diisocyanate,isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate,methylcyclohexane diisocyanate, and tetramethylxylylene diisocyanate andthe like. These compounds may also be used as mixtures.

Monofunctional isocyanates may be included to control the resinmolecular chain length such as phenyl isocyanate, tolyl isocyanate,cyclohexylisocyanate, dimethylphenyl isocyanate, butylisocyanate, andnaphthyl isocyanate are useful.

Diisocyanate substances may be partially reacted with aliphaticcompounds, alicyclic compounds, or aromatic compounds having a hydroxylgroup, an imino group, an amino group, a carboxyl group, a mercaptogroup, an epoxy group, and the like.

In the condensation reaction accompanied by decarboxylation of adiisocyanate compound, a carbodiimidization catalyst can be used. Usableas such a catalyst are, for example, phospholene oxides such as1-phenyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide,1-ethyl-2-phospholene-1-oxide, and 3-phospholene isomers thereof.

In order to convert a carbodiimide group-containing polymer into anaqueous polymer, a hydrophilic segment is provided in the molecularstructure of the carbodiimide group-containing polymer. For example, anaqueous polymer containing a carbodiimide group can be obtained byproviding a hydrophilic segment having a functional group which hasreactivity with an isocyanate group. Usable as the hydrophilic segmentare: quaternary ammonium salts of dialkylamino alkylamine (e.g.,quaternary ammonium salts of 2-dimethylaminoethanol); quaternary saltsof dialkylamino alkylamine (e.g., 3-dimethylamino-n-propylamine); alkylsulfonic acid salts having at least one reactive hydroxyl group (e.g.,sodiumhydroxypropanesulfonate); a mixture of polyethylene oxide orpolyethylene oxide, whose terminal is capped with an alkoxy group, and apolypropylene oxide (e.g., polyethylene oxide whose terminal position iscapped with a methoxygroup or an ethoxy group).

As an aqueous cross-linking agent containing an epoxy group, there areexemplified sorbitol polyglycidyl ether, glycerol triglycidyl ether,polyglycerol polyglycidylether trimethylolpropane triglycidyl ether,poly(ethyleneglycol) diglycidyl ether, poly(propyleneglycol) diglycidylether, phenol ethyleneoxide glycidyl ether, and lauryl alcoholethyleneoxide glycidyl ether or the like. In addition to the above,mentioned as examples are: a water-soluble epoxy resin obtained byreacting a carboxy compound, which is obtained through a reactionbetween a polyoxyethylene polyol compound and an acid anhydridecompound, and an epoxy resin having two or more epoxy groups in itsmolecules; and a self-emulsifiable epoxy resin composition obtained bymixing the water-soluble epoxy resin and the epoxy resin having two ormore epoxy groups in its molecules. Such resins can be obtained forexample under the tradenames of XZ 92533.00, XZ 92598.00 and XZ 92446.00from The Dow Chemical Company, Midland, Mich. Examples of the anhydridecompound include, but not particularly limited to, preferably aromaticanhydrides such as phthalic anhydride, trimellitic anhydride, andpyromellitic anhydride; and cyclic aliphatic anhydrides such as maleicanhydride, succinic anhdyride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, alkenyl succinicanhdyride, hexahydrophthalic anhydride, and methyl hexahydrophthalicanhydride. There is no limitation on the epoxy resin having two or moreepoxy groups in its molecules, and all known epoxy resins with an epoxyfunctionality of greater or equal to two can be used. Examples arepolyglycidyl ether obtained from epichlorohydrin and a polyhydriccompound such as, phenol novolac, and cresol novolac bisphenol A,bisphenol F, bisphenol S, resorcinol, hydroquinone or catechol; alkyleneoxide-added bisphenol A; polyalcohols such as polypropylene glycol,1,6-hexanediol, trimethylol propane, glycerin, cyclohexanedimethanol;and polyglycidyl ester and polyglycidyl amine of polycarboxylic acidssuch as adipic acid, phthalic acid, dimer acid and the like.

Aqueous cross-linking agent containing an isocyanate group are, forexample: polyisocyanate mainly containing at least one member selectedfrom the group consisting of an isocyanurate group-containingpolyisocyanate, an urethodione group-containing polyisocyanate, anurethodione group/isocyanurate group containing polyisocyanate, anurethane group containing polyisocyanate, an allophanate groupcontaining polyisocyanate, a biuret group containing polyisocyanate, acarbodiimide group containing polyisocyanate, and an uretodione groupcontaining polyisocyanate, each of which contains 1,6-hexamethylenediisocyanate and/or isophorone diisocyanate as a raw material; and aself-emulsifiable polyisocyanate obtained by reacting a hydrophilicsurfactant having at least one active hydrogen group which can reactwith an isocyanate group or polyethylene ether alcohol containing atleast three poly-ethylene oxide units with fatty acid ester in which thesum of the number of carbons of fatty acid and a hydroxyl containingcompound as raw materials is 8 or more and which has at least one activehydrogen group which can react with an isocyanate group. In addition tothe above, an urethane group-containing polyisocyanate obtained byreaction between 1,6-hexamethylenediisocyanate and/or an isophoronediisocyanate and an active hydrogen group-containing compound orpolyisocyanate obtained by an allophanatization reaction,carbodiimidization reaction, uretodionization reaction, andbiuretization reaction of these diisocyanate compounds can be mentioned.

Examples of suitable crosslinking agents containing an aldehyde arewaterdispersed or waterdispersible or water-soluble phenol formaldehyderesins, amino formaldehyde resins or combinations thereof.

Phenol formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with phenols. Preferred aldehdydes butnot exclusive are formaldehyde and acetaldehyde. A large variety ofphenols can be used such as but not exclusive phenol, cresol,p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol,cyclopentylphenol, cresylic acid, bisphenol-A, bisphenol-F and the likeand combinations thereof. Also acid functional phenols could be used inmaking phenol formaldehyde resins. The crosslinkers can be unetherifiedor etherified with alcohols or polyols. These phenol formaldehyde resinsmay be soluble or self-emulsifiable in water or can be stabilized by useof colloid stabilizers such as polyvinyl alcohol.

Amino formaldehyde crosslinking agents include, but are not limited to,reaction products of aldehydes with amino or amido group containingmolecules. Exemplary aldehydes include, but are not limited to,formaldehyde and acetaldehyde. A large variety of amino or amido groupcontaining molecules can be used such as but not exclusive urea,melamine, benzoguanamine, acetoguanamine, glycoluril and the like.Suitable amino crosslinking resins include melamine-formaldehyde,urea-formaldehyde, benzoguanamine-formaldehyde,acetoguanamine-formaldehyde, glycoluril-formaldehyde resins. Also themethylol groups of an amino formaldehyde resin can be partially or fullyetherified with at least one of the groups of monohydric aliphaticalcohols such as methanol and/or n-butanol. These amino formaldehyderesins may be soluble or self-emulsifiable in water or can be stabilizedby use of colloid stabilizers such as polyvinyl alcohol can be used tostabilize the amino formaldehyde dispersions.

Commercially available amino-formaldehyde resins which are water solubleor water dispersible and useful for the instant purpose include Cymel™301, Cymel™ 303, Cymel™ 370, and Cymel™ 373 (all being products of CytecSurface Specialties, Brussels, Belgium). Other aldehydes used to reactwith the amino compound to form the resinous material are crotonicaldehyde, acrolein, or compounds which generate aldehydes, such ashexamethylene-tetramine, paraldehyde, and the like.

Another class of crosslinking agents for carboxylic acid groups arewater-soluble hydroxyalkylamide crosslinkers such asBis(N,N′-dihydroxyethyl)adipamide and the like. Such compounds arecommercially available under the tradename of PRIMID™ crosslinker resinsfrom EMS-PRIMID in Switzerland, for example PRIMID™ XL-522, PRIMID™SF-4510 and PRIMID™ QM-1260

The one or more crosslinking agents may be added to the aqueousdispersion as part of the aqueous dispersion formulation process; or inthe alternative, the one or more crosslinking agents may be added to theaqueous dispersion post dispersion formulation process.

In one embodiment, depending on the type of food or beverage which is tobe contained in a coated container, and on required coating propertiesit may be beneficial to combine several crosslinkers or somecrosslinkers may be more suited than others. Some crosslinkers may notbe suited for all applications. Some crosslinkers may require theaddition of catalysts for proper cure.

Crosslinkers will help to build thermoset networks, which is indicatedby higher values of MEK Double Rubs compared to an identical formulationnot containing the crosslinker.

Forming the Dispersion

The aqueous dispersion can be formed by any number of methods recognizedby those having skill in the art. Dispersion equipment can be operatedin batch, semi-batch, or continuous mode. Examples of mixers includerotor-stator, microfluidizer, high pressure homogenizer, ultrasonic,impinging jet, Cowles™ blade, planetary mixers, and melt kneadingdevices such as extruders.

In one embodiment, one or more first polyesters, one or more stabilizingagents comprising a second polyester are melt-kneaded in an extruderalong with water and optionally one or more neutralizing agents, such asammonia, potassium hydroxide, amine, or a combination of two or more, toform a dispersion. In another embodiment, one or more first polyesters,one or more stabilizing agents comprising a second polyester arecompounded, and then melt-kneaded in an extruder in the presence ofwater, and optionally one or more neutralizing agents thereby forming adispersion. In some embodiments, the dispersion is first diluted tocontain from 1 to 20 percent, e.g., 1 to 5 percent or 1 to 3 percent, byweight of water, and then, subsequently, further diluted to comprisefrom 15 to 90 percent by weight of water, based on the weight ofdispersion. In one embodiment, further dilution may be accomplished viaa solvent. In one embodiment, the dispersion is free of any solvent.

Any melt-kneading means known in the art may be used. In someembodiments, a kneader, a BANBURY® mixer, single-screw extruder, or amulti-screw extruder, e.g. a twin screw extruder, melt pump inconnection with a rotor stator is used. A process for producing thedispersions in accordance with the present invention is not particularlylimited. For example, an extruder, in certain embodiments, for example,a twin screw extruder, is coupled to a back pressure regulator, meltpump, or gear pump. Exemplary embodiments also provide a base reservoirand an initial water reservoir, each of which includes a pump. Desiredamounts of base and initial water are provided from the base reservoirand the initial water reservoir, respectively. Any suitable pump may beused, but in some embodiments, for example, a pump that provides a flowof about 150 cc/min at a pressure of 240 bar is used to provide the baseand the initial water to the extruder. In other embodiments, a liquidinjection pump provides a flow of 300 cc/min at 200 bar or 600 cc/min at133 bar. In some embodiments, the base and initial water are preheatedin a preheater.

One or more first polyesters, in the form of, for example, pellets,powder, or flakes, are fed from the feeder to an inlet of the extruderwhere the resin is melted or compounded. One or more additionalcomponents may optionally be fed simultaneously with one or more firstpolyesters into the extruder via the feeder; or in the alternative, oneor more additional components may be compounded into one or more firstpolyesters, and then fed into the extruder via the feeder. In thealternative, additional one or more additional components may optionallyfurther be metered via an inlet prior to the emulsification zone intothe molten compound comprising one or more first polyesters. In someembodiments, the stabilizing agent comprising a second polyester isadded to one or more first polyesters through and along with the firstpolyesters and in other embodiments, the stabilizing agent comprising asecond polyester is provided separately to the twin screw extruder. Theresin melt is then delivered from the mix and convey zone to anemulsification zone of the extruder where the initial amount of waterand base from the water and base reservoirs are added through an inlet.In some embodiments, stabilizing agent comprising a second polyester maybe added additionally or exclusively to the water stream. In someembodiments, further dilution water may be added via water inlet fromwater reservoir in a dilution and cooling zone of the extruder.Typically, the dispersion is diluted to at least 30 weight percent waterin the cooling zone. In addition, the diluted mixture may be diluted anynumber of times until the desired dilution level is achieved. In someembodiments, the dispersion is further cooled after exiting the extruderby the use of a suitable heat exchanger. In other embodiments, water isnot added into the twin screw extruder but rather to a stream containingthe resin melt after the melt has exited from the extruder. In thismanner, steam pressure build-up in the extruder is eliminated and thedispersion is formed in a secondary mixing device such as a rotor statormixer.

In another embodiment, the aqueous dispersion can be formed in acontinuous high shear mixer without the use of a melt kneading extruder.In this embodiment, the first stream comprising one or more liquid ormolten first polyesters is supplied to a continuous high shear mixerfrom a suitable liquid pump for example, a syringe pump, gear pump, orprogressive cavity pump. The first stream is flowed through a firstconduit and merged continuously with a second stream containing acontinuous aqueous phase that is flowed through a second conduit. Thefirst and second streams are merged into a disperser in the presence ofa stabilizing agent comprising a second polyester with optionalneutralizing agent. The agents can be added to either the first orsecond stream, or as a separate stream. A third stream comprising watercan be added downstream from the disperser. The flow rates of thestreams are adjusted to achieve a dispersion having the desired amountof polymer phase and percent solids. The disperser can be any one of anumber of continuous inline mixers, for example, an IKA high-shearmixer, Oakes rotor stator mixer, Ross mixer, Silverson mixer, orcentrifugal pump. The rpm setting of the disperser can be used to helpcontrol the particle size of the dispersed hydrophobic phase in thedispersion. The system can be heated to provide the polymer andneutralizer components at a suitable viscosity for pumping. Steamformation is reduced by controlling the pressure through the use of abackpressure regulator, gear pump, metering pump, or other suitabledevice near the exit of the process. In some embodiments, the dispersionis further cooled after exiting the disperser by the use of a suitableheat exchanger.

In another embodiment, the aqueous dispersion can be formed in a batchor semi-batch high shear mixer where the mixer may, for example, bedisposed within a pressurized tank to, for example, reduce steamformation. All or at least a portion of the dispersion is removed fromthe tank during processing, and optionally cooled by the use of asuitable heat exchanger.

During the preparation of the aqueous dispersion, optionally one or morefillers; optionally one or more additives such as catalysts, wettingagents, defoamers, flow agents, release agents, slip agents,anti-blocking agents, additives to mask sulfur staining, pigmentwetting/dispersion agents, anti-settling agents, UV stabilizers,adhesion promoters; optionally one or more lubricants such as fatty acidester wax, silicon-based wax, fluorine-based wax, polyethylene or anyother similar polyolefin wax, carnauba wax, lanolin wax or the like;optionally one or more corrosion inhibitors such as aluminum, and zinc:optionally one or more pigments, e.g. titanium dioxide, mica, calciumcarbonate, barium sulfate, silica, zinc oxide, milled glass, aluminumtrihydrate, talc, antimony trioxide, fly ash, and clay or the like;optionally one or more dyes; optionally one or more co-solvents, e.g.glycols, glycol ether, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate,alcohols, mineral spirits, and benzoate esters or the like; optionallyone or more dispersants, e.g. aminoalcohols, and polycarboxylates;optionally one or more surfactants; optionally one or more defoamers;optionally one or more preservatives, e.g. biocides, mildewcides,fungicides, algaecides, and combinations thereof; optionally one or morethickeners, e.g. cellulosic based thickeners such as hydroxyethylcellulose, hydrophobically modified alkali soluble emulsions (HASEthickeners such as UCAR POLYPHOBE TR-116) and hydrophobically modifiedethoxylated urethane thickeners (HEUR); or optionally one or moreadditional neutralizing agents, e.g. hydroxides, amines, ammonia, andcarbonates may be added to the aqueous dispersion formulation; or in thealternative, may be added to the dispersion post dispersion formulationprocess.

During the preparation of the aqueous dispersion, one or morecrosslinking agents may also be added to the aqueous dispersionformulation; or in the alternative, may be added to the dispersion postdispersion formulation process.

Optionally during the dispersion of the one or more first polyesters,another polymer dispersion or emulsion may be used as a portion of theaqueous phase of the dispersion. Examples include, but are not limitedto, acrylic, epoxy, polyester, polyurethane, polyolefin, polyamide,alkyd, and the like containing dispersions, emulsions, suspensions,colloidal suspensions.

In one embodiment, the method for producing the inventive aqueousdispersion comprises the steps of: (1) selecting one or more firstpolyesters having an acid number in the range of from less than 15, forexample less than 10, or in the alternative less than 5; (2) selectingone or more stabilizing agents comprising at least one second polyesterhaving an acid number equal to or greater than 15, for example greaterthan 20; (3) selecting one or more neutralizing agents; (4)melt-blending said one or more first polyesters, one or more stabilizingagents in the presence of water and one or more neutralizing agents; (4)thereby producing an aqueous dispersion having a solid content of 10 to74 percent, based on the total weight of the dispersion.

Coating Applications and Forming Coated Containers or Closure Devices

The aqueous dispersion and/or coating composition derived therefrom maybe used on any suitable substrate including, but not limited to metal,wood, paper, plastic, leather, glass, concrete, and the like. In oneembodiment the aqueous dispersion and/or coating derived therefrom maybe used, for example, in container, e.g. can, coating application, orclosure device coating application. Such coated container devicesinclude, but are not limited to, cans such as beverage cans, food cans;aerosol containers such as those for non-food products, e.g. hair spray,hair dye, or color spray lacquers; drums; kegs; pails; decorative tins;open trays; tubes, bottles, monoblocs, and the like. The coated articlessuch as closure devices include, but are not limited to, caps, lids suchas thin aluminum foil based lids for yogurt and butter containers, orcrown corks; closures for glass jars and bottles such as roll-onclosures, vacuum closures, pilfer-proof closures, easy peel lids for canclosures, and easy open end or conventional ends for cans. Cans may be 2piece cans or 3 piece cans. Beverage cans include, but are not limitedto, beer cans, carbonated soft drink cans, energy drink cans, isotonicdrink cans, water cans, juice cans, tea cans, coffee cans, milk cans,and the like. Food cans, include, but are not limited to, vegetablecans, fruit cans, meat cans, soup cans, ready meal cans, fish cans,edible oil cans, sauce cans and the like. Such cans may have any shapes;for example, such can may have a cylindrical shape, cubical, spherical,semi-spherical, bottle shape, elongated cubical shape, shallow or tallshape, round or rectangular shape or any other suitable shape. Thecoated articles such as container devices according to the instantinvention may be formed via any conventional method. For example, thecoated container device may be formed via stamping, drawing, redrawing,wall ironing, bending, beading, embossing, debossing, flanging, necking,stretching, blow-stretching and any other suitable conventional method.Such methods are generally known to those having ordinary skill in theart. The aqueous dispersion and/or coating composition derived therefrommay, for example, be applied to a substrate, e.g. metal sheet or metalfoil, and then the coated substrate may be formed into a coatedcontainer device or a coated closure device. In the alternative, asubstrate may be formed into a container device or a closure device, andthen the container device or the closure device is coated with one ormore aqueous dispersions and/or coating composition derived therefrom toform the coated container device or coated closure device. The coatingmay be applied via any method; for example, via roller coating, spraycoating, powder coating, dip coating, electrodeposition coating,printing, wash coating, flow coating, curtain coating.

The substrate comprises one or more metals including, but not limitedto, aluminum and aluminum alloys, electrolytic tinplate cold rolled lowcarbon mild steel (“ETP”), electrolytic chromium/chromium oxide coatedcold rolled low carbon mild steel (ECCS), and any other pre-treatedsteel, or one or more polymers such as one or more polyolefins, e.g.polyethylene and/or polypropylene. Pretreatment may include, but is notlimited to, treatment with phosphoric acid, zirconium phosphate,chromium phosphate, and the like as well as silanes for reasons such asprimary corrosion protection and improved adhesion. The substrate maycomprise a sheet, strip or a coil. The substrate may comprise one ormore layers, and each layer may have a thickness in the range of from0.01 μm to 2 mm; for example, from 0.01 μm to 1.5 mm; or in thealternative, from 0.01 μm to 1 mm; or in the alternative, from 0.01 μmto 0.5 mm; or in the alternative, from 0.01 μm to 0.2 mm; or in thealternative, from 0.01 μm to 0.1 mm or in the alternative, from 0.01 μmto 100 μm; or in the alternative, from 0.01 μm to 50 μm; or in thealternative, from 1 μm to 50 μm; or in the alternative, from 1 μm to 15μm. The substrate may be pre-coated with one or more pre-coatingcompositions. Such pre-coating compositions may optionally furtherinclude, but are not limited to, one or more resin binders, one or moreresin crosslinkers, one or more solvents, one or more additives, and oneor more pigments. Exemplary resin binders include, but are not limitedto, epoxy, polyester, polyvinyl chloride containing organosols/vinyls,phenolic, alkyd, oleoresin, acrylic resin, and the like. Exemplarycrosslinkers include, but are not limited to, phenol-formaldehyderesins; amino-formaldehyde resins including but not limited tourea-formaldehyde, melamine formaldehyde, benzoguanamine formaldehyde;anhydride resins, blocked isocyanate resins and epoxy groups containingresins, including but not limited to, epoxy resins, epoxy groupscontaining polyesters, acrylic resins, vinyl resins or the like.Exemplary solvents and thinners include, but are not limited to, glycolethers, alcohols, aromatics, e.g. aromatic hydrocarbons, white spirit,branched ketones and esters. Exemplary additives include, but are notlimited to, catalysts, lubricants, wetting agents, defoamers, flowagents, release agents, slip agents, anti-blocking agents, additives tomask sulfur staining, pigment wetting/dispersion agents, anti-settlingagents, UV stabilizers, adhesion promoters. Pigments include, but arenot limited to titanium dioxide, zinc oxide, aluminum oxide, zinc andaluminum. The substrate may also be pre-coated with one or morepre-coated laminate compositions. Such compositions may, for example,include polyethylene, polypropylene, or polyester compositions, and maybe applied either as a film via film lamination process ormelt-extrusion coating process onto the metal surface.

The one or more aqueous dispersions and/or coating composition derivedtherefrom applied to the at least one surface of the substrate may bedried via any conventional drying method. Such conventional dryingmethods include but, are not limited to, air drying, convection ovendrying, hot air drying, and/or infrared oven drying. During the dryingprocess, crosslinking of one or more base polymers, stabilizing agents,or combinations thereof, involving one or more the crosslinking agents,may occur. Additional cure might occur by radiation cure, e.g.electron-beam cure. The one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be dried at any temperature; for example, it may be driedat a temperature in the range of equal or greater than the melting pointtemperature of the first polyester; or in the alternative, it may bedried at a temperature in the range of less than the melting point ofthe stabilizing agent comprising a second polyester. The one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be dried at atemperature in the range of about 60° F. (15.5° C.) to about 700° F.(371° C.) for a period of less than about 40 minutes, for example, lessthan 20 minutes, or less than 10 minutes, or less than 5 minutes, orless than 2 minutes, or less than 1 minute, or less than 20 seconds. Allindividual values and subranges from about 60° F. (15.5° C.) to about700° F. (371° C.) are included herein and disclosed herein; for example,the one or more aqueous dispersions and/or coating composition derivedtherefrom applied to the at least one surface of the substrate may bedried at a temperature in the range of about 60° F. (15.5° C.) to about500° F. (260° C.) for a period of less than about 40 minutes, forexample, less than 20 minutes, or less than 10 minutes, or less than 5minutes, or less than 2 minutes, or less than 1 minute, or in thealternative, the one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be dried at a temperature in the range of about 60° F.(15.5° C.) to about 450° F. (232.2° C.) for a period of less than about40 minutes, for example, less than 20 minutes, or less than 10 minutes,or less than 5 minutes, or less than 2 minutes, or less than 1 minute.The temperature of the one or more aqueous dispersions and/or coatingcomposition derived therefrom applied to the at least one surface of thesubstrate may be raised to a temperature in the range of equal orgreater than the melting point temperature of the base polymer for aperiod of less than about 40 minutes. All individual values andsubranges from less than about 40 minutes are included herein anddisclosed herein; for example, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period of less than about 20minutes, or in the alternative, the temperature of the one or moreaqueous dispersions applied and/or coating composition derived therefromto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period of less than about 5minutes, or in another alternative, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of equal or greater than the melting pointtemperature of the first polyester for a period in the range of about0.5 to 300 seconds. In another alternative, the temperature of the oneor more aqueous dispersions and/or coating composition derived therefromapplied to the at least one surface of the substrate may be raised to atemperature in the range of less than the melting point temperature ofthe first polyester for a period of less than 40 minutes. All individualvalues and subranges from less than about 40 minutes are included hereinand disclosed herein; for example, the temperature of the one or moreaqueous dispersions and/or coating composition derived therefrom appliedto the at least one surface of the substrate may be raised to atemperature in the range of less than the melting point temperature ofthe first polyester for a period of less than about 20 minutes, or inthe alternative, the temperature of the one or more aqueous dispersionsand/or coating composition derived therefrom applied to the at least onesurface of the substrate may be raised to a temperature in the range ofless than the melting point temperature of the first polyester for aperiod of less than about 5 minutes, or in another alternative, thetemperature of the one or more aqueous dispersions applied and/orcoating composition derived therefrom to the at least one surface of thesubstrate may be raised to a temperature in the range of less than themelting point temperature of the first polyester for a period in therange of about 0.5 to 300 seconds.

The coated substrate may further be coated with one or more conventionalcoating compositions, or it may further be laminated to one or moreother layers. Such conventional coating compositions are generally knownto person of ordinary skill in the art, and they may include, but arenot limited to, epoxy resin coating compositions, acrylate based coatingcompositions, and polyester based coating compositions. The laminationprocess is generally known, and exemplary lamination layers may include,but are not limited to, polyester laminates, polyolefin based laminatessuch as polypropylene laminates.

The one or more aqueous dispersions and/or coating composition derivedtherefrom applied to at least one surface of a substrate, for example apre-coated substrate, as one or more crosslinked coating layers may havea cross cut adhesion, before retort, rating of at least 3B; for example,4 B or 5B, measured according to ASTM-D 3359-08. The one or more aqueousdispersions and/or coating composition derived therefrom applied to atleast one surface of a substrate as one or more crosslinked coatinglayers may have a wedge bend pass rating of at least 50 percent, forexample, at least 70 percent, or in the alternative, at least 80percent, or in the alternative, at least 90 percent, measured via aGardner “COVERALL” Bend Tester IG 1125.

EXAMPLES

The following examples illustrate the present invention but are notintended to limit the scope of the invention. The examples of theinstant invention demonstrate that the one or more aqueous dispersionsapplied to at least one surface of a metal substrate provide forimproved coating layer flexibility as well as coating layer adhesion tothe metal substrate.

Description of Formulation Components

Dynapol L952 is a saturated linear aromatic polyester having a T_(g) ofapproximately 70° C., a molecular weight of 18000 g/mol, an acid numberof 2 mg KOH/g, and a hydroxyl number of 6 mg KOH/g, available fromEvonik Industries.

Dynapol L912 is a saturated linear aromatic polyester having a T_(g) ofapproximately 105° C., acid number <3 mg KOH/g, OH number ˜5 mg/g KOH/g,and a molecular weight of 15000 g/mol, available from Evonik Industries.

Dynapol LS615 is an aliphatic polyester having a T_(g) of approximately−50° C., a molecular weight of 4000 g/mol, an acid number of <2 mgKOH/g, and a hydroxyl number of 26 mg KOH/g, available from EvonikIndustries.

Crylcoat 1510 is an aromatic polyester having a T_(g) of approximately58° C., a melt viscosity of 8500 Poise at 200 C, an acid number of 71 mgKOH/g, and a hydroxyl number of <2 mg KOH/g, available from Cytec.

Finetone T382ES is a bisphenol-A fumarate (aromatic, linear) polyesterwith an acid number of 21 mg KOH/g, a T_(g) of approximately 56° C.,available from Reichhold.

Tego Addbond 1270 is a polyester with an acid number of 60 mg KOH/g anda hydroxyl number of 10 mg KOH/g, available from Evonik Tego ChemieGmbH.

Primacor 5980i (CAS No. 9010-77-9) is an ethylene acrylic-acid copolymerhaving acrylic acid content of approximately in the range of 19.5 to21.5 weight percent, and a melt index of approximately 300 g/10 minutes(ASTM D 1238, 190° C./2.16 Kg), available from The Dow Chemical Company.

CYMEL 303 crosslinking agent is a commercial grade ofhexamethoxymethylmelamine supplied in liquid form at >98% non-volatile.It is a clear viscous liquid with a viscosity of 2600-5000 centipoise,available from CYTEC.

NACURE 5925 is an amine neutralized DDBSA catalyst, uses as heatinitiated catalyst catalyzing the crosslinking between the polyester andthe crosslinker. It is a clear, light amber liquid supplied as 25%active. The recommended use level is 0.5 to 2.0% as supplied on totalresin solids, available from King industries.

Preparation of Inventive Aqueous Dispersions A, B, & C, and ComparativeDispersion F

Inventive aqueous dispersion examples A, B, & C and Comparativedispersion example F were prepared according to the following proceduresbased on the formulation components listed in Tables 1 and 2. The firstpolyester, and stabilizing agent were fed into a 25 mm diameter twinscrew extruder by means of separate controlled rate feeders. In theextruder the first polyester and stabilizing agent were melted, mixedand forwarded. The extruder temperature profile was initially set to150° C. prior to the addition of the initial water and neutralizingagent. After the addition of initial water and neutralizing agent thetemperature was lowered to 120° C. across the barrel. In these examplesDMEA, 2-dimethyl amino ethanol (100%) (CAS No. 108-01-0) was used as theneutralizing agent. The extruder speed was approximately 450 rpm. Aminebase and initial water were mixed together and fed to the extruder atthe initial water introduction point. The dilution water was fed via asecond pump, and it was introduced into the dilution zone of theextruder. The initial water and dilution water streams were optionallypre-heated to the extruder temperature. At the extruder outlet, aback-pressure regulator was used to adjust to a suitable pressure insidethe extruder barrel to prevent steam formation at the operatingtemperature. The resulting dispersions were cooled and filtered througha 200 micron filter. Inventive aqueous dispersion examples A, B, & C,and comparative dispersion example F were tested for their properties,and the results are reported in Table 3.

Preparation of Inventive Aqueous Dispersion Example D

Inventive aqueous dispersion example D was prepared according to thefollowing procedures based on the formulation components listed in Table1 and 2. The first polyester and stabilizing agent were fed into a 25 mmdiameter twin screw extruder by means of separate controlled ratefeeders. The Tego Addbond 1270 was devolatilized to remove thesec-butanol solvent from its commercially available form, and wascryogenically ground into 100% active chunks, which were supplied intothe extruder by the controlled rate feeder. In the extruder the firstpolyester and stabilizing agent were melted, mixed and forwarded. Theextruder temperature profile was initially set to 150° C. prior to theaddition of the initial water and neutralizing agent. After the additionof initial water and neutralizing agent the temperature was lowered to120° C. across the barrel. In this example DMEA, 2-dimethyl aminoethanol (100%) (CAS No. 108-01-0) was used as the neutralizing agent.The extruder speed was approximately 450 rpm. Amine base and initialwater were mixed together and fed to the extruder at the initial waterintroduction point. The dilution water was fed via a second pump, and itwas introduced into the dilution zone of the extruder. The initial waterand dilution water streams were optionally pre-heated to the extrudertemperature. At the extruder outlet, a back-pressure regulator was usedto adjust to a suitable pressure inside the extruder barrel to preventsteam formation at the operating temperature. The resulting dispersionwas cooled and filtered through a 200 micron filter. Inventive aqueousdispersion example D was tested for its properties, and the results arereported in Table 3.

Preparation of Comparative Dispersion Example E

Comparative dispersion example E was prepared according to the followingprocedures based on the formulation components listed in Table 1 and 2.The liquid first polyester, and the melted stabilizing agent werecombined and fed into a 4 inch diameter rotor stator mixer (manufacturedby E.T. Oakes Corporation) by means of a controlled rate feeder. In themixer, the first polyester and stabilizing agent were combined withinitial water and neutralizing agent. In this example DMEA, 2-dimethylamino ethanol (100%) (CAS No. 108-01-0) was used as the neutralizingagent. The first polyester/stabilizing agent feed and the Oakes mixerwere both temperature controlled to a set point of 150° C. After theaddition of the initial water and neutralizing agent, the process lineswere temperature controlled to a set point of 100° C. The mixer speedwas set to 750 rpm for this example. The dilution water was fed via asecond pump, and it was introduced to the process in a second Oakesmixer. The initial water and dilution water streams were optionallypre-heated to the line temperature at the point of delivery to theprocess. At the process outlet, a back-pressure regulator was used toadjust to a suitable pressure inside the process to prevent steamformation at the operating temperature. The resulting dispersion wascooled and filtered through a 200 micron filter. Comparative aqueousdispersion example E was tested for its properties, and the results arereported in Table 3.

TABLE 1 Stabilizing Agent Avg. Average Comprising Polymer InitialDilution Particle First Second Phase Neutralizing Water Water SizeAqueous Polyester Polyester Acid Agent Rate Rate Diameter Dispersion(g/min) (g/min) Number (ml/min) (ml/min) (ml/min) (microns) InventiveDynapol Crylcoat 15.8 DMEA 11.6 65 0.5 Example A L952 1510 (2.6)  (60.5)(15.1) Inventive Dynapol Finetone  5.8 DMEA 9.1 67 1.1 Example B L952T382ES (1.5)  (55.1) (13.8) Inventive Dynapol Crylcoat 16.6 DMEA 9.71 751.4 Example C L912 1510 (3.41) (60.5) (15.1) Inventive Dynapol Tego 13.6DMEA 11.8 75 1.2 Example D L952 Addbond (2.5)  (48.4) 1270 (12.1)Comparative Dynapol Crylcoat  8.9 DMEA 15 30 6.8 Example E LS615 1510(1.11) (45.0) (5.0) Comparative Dynapol Primacor 32.6 DMEA 17.7 70 NoExample F L952 5980i (5.5)  dispersion (60.5) (15.1)

TABLE 2 Stabilizing Agent Comprising Neutralizing Aqueous FirstPolyester Second Polyester Agent Water Dispersion (w %) (w %) (w %) (w%) Inventive 39.1 9.8 1.7 49.4 Example A Inventive 37.6 9.4 1.0 52.0Example B Inventive 37.0 9.2 2.1 51.7 Example C Inventive 32.3 8.1 1.757.9 Example D Comparative 46.8 5.2 1.2 46.8 Example E Comparative 35.88.9 3.3 52.0 Example F

TABLE 3 Average Particle Size Aqueous Total % Diameter Dispersion solids% Neutralization pH (microns) Inventive 49.42% 120% 8.12 0.5 Example AInventive 49.82% 210% 8.82 1.1 Example B Inventive 49.08% 120% 9.12 1.4Example C Inventive 46.52% 150% 9.54 1.2 Example D Comparative Not 130%Not 6.8 Example E measured measured Comparative No 120% No No Example Fdispersion dispersion dispersion

Melt blends of the first and second polyesters were prepared in order toassess their compatibility and suitability for preparing a stabledispersion with particle size of less than 5 micron as described below.

Preparation of Melt Blends of First and Second Polyesters Examples H, I,& J, and Comparative Example L

Inventive melt blend examples H, I, & J, and comparative blend examplesL were prepared according to the following procedures based on theformulation components listed in Table 4. The first polyester, andstabilizing agent were fed into a 25 mm diameter twin screw extruder bymeans of separate controlled rate feeders. In the extruder the firstpolyester and stabilizing agent were melted, mixed and forwarded. Theextruder temperature profile was set to 150° C. Inventive melt blendexamples H, I, & J, and comparative melt blend example L were collectedat the extruder outlet, and tested for their properties. The results arereported in table 4.

Preparation of Comparative Melt Blend of Polyester Example K

Comparative dispersion example K was prepared according to the followingprocedure. The Crylcoat 1510 stabilizing agent was fed into a 25 mmdiameter twin screw extruder by means of a controlled rate feeder at arate of 10 g/min. First polyester, Dynapol LS615, was supplied as aliquid to the melt zone of the extruder at a rate of 30 g/min where itwas mixed and forwarded with the stabilizing agent. The extrudertemperature profile was initially set to 130° C. and reduced to 80 Cafter all the flows were initialized. The comparative melt blend exampleK was collected at the extruder outlet, and tested for its properties.The results are reported in table 4.

As shown in Table 4, inventive blends H, I, and J, resulted in asemi-clear/amber melt blend, while the comparative examples K & Lresulted in opaque, dull, or hazy white blends, indicating poorcompatibility between the first and second polyesters. When dispersionswere subsequently produced from inventive blends H, I, and J, excellentstable dispersions with small particle size were produced, while nostable dispersion could be produced from comparative example blend L,and comparative example blend K produced a very poor dispersion withlarge particle size.

TABLE 4 Resultant Dispersion Avg. First Stabilizing Particle Size MeltBlend Melt Blend Polyester Agent (microns) Appearance Inventive DynapolCrylcoat 0.5 Semi-clear Example H L952 1510 amber Inventive DynapolFinetone 1.1 Semi-clear Example I L952 T382ES amber Inventive DynapolCrylcoat 1.4 Semi-clear Example J L912 1510 amber Comparative DyapolCrylcoat 6.8 Opaque dull Example K LS615 1510 white Comparative DynapolPrimacor No Opaque bright Example L L952 5980 dispersion whitePreparation of Inventive Coating Compositions 1-10

Inventive Aqueous dispersion Examples A, B, C, and D were mixed withCymel™ 303LF, hexamethoxymethylmelamine resin (Cytec Industries), as acrosslinking agent, Nacure 5925, amine neutralized dodecylbenzenesulfonic acid (King Industries), as a catalyst, and additional water toreduce solids in a 2 oz. glass jar using a tumbler at room temperature,approximately 25° C., overnight (18-24 hrs) to yield the inventivecoating compositions 1-10. Coatings formulations for inventive coatingcompositions 1-10 are listed in Table 5.

TABLE 5 Inven- Inven- Total Total tive tive Disper- Cymel Nacure Formu-Formu- Coating Disper- sion 303LF 5925 Water lation laion Compo- sionAmount Amount Amount Amount Amount % sition Example (g) (g) (g) (g) (g)Solids 1 A 40.00 2.30 0.12 0.00 42.42 54.57 2 A 40.00 5.18 0.13 2.4147.72 54.57 3 A 40.00 8.88 0.15 5.51 54.54 54.57 4 A 40.00 13.82 0.179.64 63.63 54.57 5 B 40.00 1.05 0.10 0.00 41.15 51.23 6 C 40.00 1.030.10 0.00 41.13 50.49 7 C 40.00 2.18 0.11 0.00 42.29 51.84 8 D 40.007.97 0.13 0.00 48.10 55.53 9 D 20.00 0.49 0.05 0.00 20.54 47.92 10 D20.00 1.04 0.05 0.00 21.09 49.27Preparation of Comparative Coating Compositions 11 and 12

Dynapol L952 was dissolved into a 1:1 blend by weight of toluene and PMacetate (1-methoxy-2-acetoxypropane) at 70° C. to produce a 40% weightsolids solution. This procedure was performed in 5 liter round bottomflask, equipped with reflux condenser, under constant agitation with arod stirrer and a heating mantle, resulting in ˜3500 g of solution.After cooling to room temperature (˜25° C.), this solution was thenmixed with Cymel™ 303LF, hexamethoxymethylmelamine resin (CytecIndustries), as a crosslinking agent, Nacure 5925, amine neutralizeddodecylbenzene sulfonic acid (King Industries), as a catalyst, and PMacetate to reduce solids in a 2 oz. glass jar using a tumbler at roomtemperature, approximately 25° C., overnight (18-24 hrs) to yieldcomparative coating compositions 11. Dynapol L952 solvent based solutionwas mixed with Cymel™ 303LF, Crylcoat 1510-0, DMEA, for amineneutralization, Nacure 5925, and PM acetate to reduce solids in a 2 oz.glass jar using a tumbler at room temperature, approximately 25° C.,overnight (18-24 hrs) to yield comparative coating compositions 12.Coating formulations for comparative coating compositions 11 and 12 arelisted in Table 6.

TABLE 6 Dynapol L952 SB Crylcoat Cymel Nacure Extra Total ComparativeSolution 1510-0 303LF DMEA 5925 PMA Formulation Total Coating AmountAmount Amount Amount Amount Amount Amount Formulaion Compsotion (g) (g)(g) (g) (g) (g) (g) % Solids 11 25.00 0.00 4.29 0.00 0.07 18.50 47.8630.00 12 25.00 2.50 4.29 0.28 0.09 25.74 57.90 29.64Coating Application

A tin plate panel, provided by Rasselstein, having grade TS-245 standardfinish, with approximately 10 cm to 20 cm size was cleaned with acetone,and then dried. About 3 grams of the various coating compositions wereapplied individually to the tin plate panel via a 35 micron (1.4 mil#14) wirewound drawdown bar thereby coating one surface of the tin platepanel. Subsequently, the panel was placed into a convection oven to becured for 10 minutes at 200° C. The coated tin plate panels were testedfor wedge bend, cross cut adhesion before sterilization, and cross cutadhesion and blush after sterilization according to the proceduresdescribed below. Aluminum panels (can stock clean aluminum measuring0.009×4″×12″ from All Foils), cleaned with acetone and dried, were usedfor coating thickness and MEK DR (methyl ethyl ketone double rub)evaluation. The results are reported in Table 7 and 8.

TABLE 7 Crosscut Crosscut Wedge Adhesion Adhesion Retort Coating CoatingMEK Bend Before After Resis- Compo- Thickness Double (% Retort Retorttance sition (mil) Rubs Pass) in Water in Water in Water 1 0.35-0.45150+ 100 5B 5B 3 2 0.35-0.45 150+ 94 5B 5B 3 3 0.35-0.45 150+ 88 5B 1B 34 0.35-0.45 150+ 77 5B 5B 3 5 0.20-0.35 25 86 5B 0B 4 6 0.24-0.30 40 685B 5B 3 7 0.24-0.30 150+ 100 5B 5B 3 8 0.36-0.44 150+ 90 5B 0B 2 90.35-0.45 25 90 5B 0B 4 10 0.30-0.40 150+ 73 5B 0B 3 13 0.35-0.45 65 845B 5B 5 14 0.35-0.45 60 76 5B 5B 4

TABLE 8 Crosscut Adhesion Crosscut Adhesion Retort Coating Before Retortin After Retort in Resistance Composition Lactic Acid Lactic Acid inLactic Acid 1 5B 5B 3 2 5B 5B 3 3 5B 3B 3 4 5B 0B 3 5 5B 2B 3 6 5B 5B 37 5B 5B 3 8 5B 0B 4 9 5B 0B 4 10 5B 0B 4 13 5B 0B 4 14 5B 2B 4

Test Methods

Test methods include the following:

Particle Size Measurement

The average particle size was measured by a Coulter LS-230 particle sizeanalyzer (Beckman Coulter Corporation).

Cross-Cut Adhesion Before Retort

Cross-cut adhesion is measured according to ASTM-D 3359-02, measuringadhesion by tape test, Method B., using an Erichsen cross-cut tester EPT675R. This method provides the procedure for assessing the adhesion ofcoating films to metallic substrates by applying and removing a tape(grade: TESA 4124 clear) over the cuts made in the film. Place thecentre of a piece of tape over the grid and in the area of the gridsmooth into place by a finger. To ensure good contact with the film rubthe tape firmly. Within 90±30 seconds of application, remove the tape byseizing the free end and rapidly (not jerked) pulling it off at as closeto an angle of 180 degrees as possible. Inspect the grid area forremoval of coating from the substrate or from a previous coating usingthe illuminated magnifier. Rate the adhesion in accordance with thefollowing scale rating:

5B The edges of the cuts are completely smooth; none of the squares ofthe lattice is detached. 4B Small flakes of the coating are detached atintersections; less than 5% of the area is affected. 3B Small flakes ofthe coating are detached along the edges and at intersections of cuts.The area affected is 5-15% of the lattice. 2B The coating has flakedalong the edges and on parts of the squares. The area affected is 15-35%of the lattice. 1B The coating has flaked along the edges of cuts inlarge ribbons and whole squares have detached. The area affected is35-65% of the lattice. 0B Flaking and detachment is worse than 1BCross-Cut Adhesion after Retort

In addition to testing cross cut adhesion on the dry panels prior towater retort exposure, a cross-cut adhesion test is performed within anhour of being removed from the autoclave and rated for adhesion asdescribed in the cross cut adhesion section. The adhesion is rated inaccordance with the following scale rating:

5B The edges of the cuts are completely smooth; none of the squares ofthe lattice is detached. 4B Small flakes of the coating are detached atintersections; less than 5% of the area is affected. 3B Small flakes ofthe coating are detached along the edges and at intersections of cuts.The area affected is 5-15% of the lattice. 2B The coating has flakedalong the edges and on parts of the squares. The area affected is 15-35%of the lattice. 1B The coating has flaked along the edges of cuts inlarge ribbons and whole squares have detached. The area affected is35-65% of the lattice. 0B Flaking and detachment is worse than 1BRetort Resistance (Water)

The coated panels were immersed in water in individual pressurizableglass beakers that were contained in a secondary container tray, andplaced into a Tuttnauer 10″ dia×18″ Deep Chamber Autoclave model 1Z-TUT-EZ-10 where they were retorted at 129° C. for 30 minutes. Thepanels were removed, and dried. The coating appearance was then rated ona scale of 1-5 (5—best, 1—worst) as determined by blush (a whitishappearance of the coating). as shown below.

5 No Blush 4 Very Slight blush 3 Slight blush 2 Blush 1 Strong BlushRetort Resistance (Lactic Acid)

The coated panels were immersed in 2% lactic acid in individualpressurizable glass beakers that were contained in a secondary containertray, and placed into a Tuttnauer 10″ dia×18″ Deep Chamber Autoclavemodel 1 Z-TUT-EZ-10 where they were retorted at 121° C. for 30 minutes.The panels were removed, and dried. The coating appearance was thenrated on a scale of 1-5 (5—best, 1—worst) as determined by blush (awhitish appearance of the coating) as shown below.

5 No Blush 4 Very Slight blush 3 Slight blush 2 Blush 1 Strong BlushMEK Double Rub

The round end of a 1.5 pound ball peen hammer was used to perform theMEK double rub test by applying a force of ˜1000-2000 g to the coating.A 4″×4″ square of cheesecloth was bound around the hammer end and soakedwith methyl ethyl ketone (MEK). The hammer was brought into contact withthe coating, and moved forth-and-back over a section measuringapproximately 6″×1″, wherein one movement forth-and-back over the wholecoating is considered one double rub. Double rubs were performed at arate of about one double rub per second. No additional pressure wasapplied onto the hammer. After every 25 double rubs, the tissue wasre-soaked. The double rub step was repeated until the coating was rubbedoff, i.e. at least a portion of the metal substrate was exposed(excluding the ½″ end sections of the testing area). In the event thatthe double rub step reached 150 double rubs, the testing was terminated,and 150+ double rubs were reported as the final results.

Wedge Bend

Wedge bend was measured via Gardner “COVERALL” Bend Tester IG 1125. Theapparatus used for this test consists of two parts to convert it to abending machine. A steel rod (mandrel) is mounted at the front of thebase. The coated test panel of 100 mm width was flexed over the 3 mm rodmandrel; thus, the coating appears on the outside of the bend. Theflexed panel was inserted in the wedge mandrel. The impacter, i.e. ametal weight, was raised to 40 centimeters height, and then dropped. Theimpacter is retrieved on its first bounce, and secured. The cylindricalfold in the panel was squeezed into a conical shape. The edge of thecoated panel was rubbed with a solution of copper sulfate (mixture of 10grams of copper sulfate, 90 grams of water and 3 grams of sulfuricacid). Anywhere the coating had been cracked; dark spots appeared,indicating failure. The length of the intact area along the length ofthe wedge bend, which is 100 mm, was measured in millimeters andexpressed as percent ok.

Coating Thickness

Coating thickness was measured according to ASTM-D 1186-93,non-destructive measurement of dry film thickness of non magneticcoatings applied to a non-ferrous base, using a Byko-Test 8500 coatingthickness gauge. The standard aluminum panel without any coating wasused for calibration. The thickness of the coating of the coated panelswas reported as the range of 10 measurements, wherein each measurementof the thickness of the coating of the coated panels was measured usinga probe for non-ferrous materials relative to the thickness of thecoating of the standard panel, i.e. zero. The measured thickness wasreported in mils.

The present invention may be embodied in other forms without departingfrom the spirit and the essential attributes thereof, and, accordingly,reference should be made to the appended claims, rather than to theforegoing specification, as indicating the scope of the invention.

1. An aqueous dispersion comprising the melt blending product of: (a)from 50 to 99 percent by weight of one or more first polyesters, basedon the total solid content of the dispersion, wherein said one or morefirst polyesters have an acid number in the range of from less than 15,based on the total solid content of the one or more first polyesters;(b) from 1 to 50 percent by weight of one or more stabilizing agentscomprising at least one second polyester, based on the total solidcontent of the dispersion, wherein said second polyester has acarboxylic acid group and an acid number equal to or greater than 15,based on the solid content of the second polyester; (c) one or moreneutralizing agents; and (d) from 15 to 90 percent by weight of water,based on the total weight of the dispersion; wherein said dispersion hasa solid content of 10 to 85 percent, based on the total weight of thedispersion, and wherein the volume average particle size of thedispersion is less than 5 microns.
 2. A method for producing a aqueousdispersion comprising the steps of: selecting one or more firstpolyesters having an acid number in the range of from less than 15,based on the total solid content of the one or more first polyesters;selecting one or more stabilizing agents comprising at least one secondpolyester having an acid number equal to or greater than 15, based onthe solid content of the second polyester; selecting one or moreneutralizing agents; melt-blending said one or more first polyesters,one or more stabilizing agents in the presence of water and one or moreneutralizing agents; thereby producing an aqueous dispersion having asolid content of 10 to 85 percent, based on the total weight of thedispersion, and wherein the volume average particle size of thedispersion is less than 5 microns.
 3. A coating composition comprising:the aqueous dispersion of claim 1; optionally one or more cross-linkingagents; optionally one or more cross-linking catalysts; optionally oneor more solvents; optionally one or more selected from the groupconsisting of a polyolefin dispersion, acrylic latex, epoxy resindispersion, polyurethane dispersion, alkyd dispersion, vinyl acetatedispersion, and ethylene vinyl acetate dispersion; and optionally one ormore additives.
 4. A coating comprising: at least one or more filmlayers derived from the dispersion of claim 1 or the coating compositionof claim
 3. 5. A coated article comprising: one or more substrates; atleast one or more coating layers derived from the dispersion of claim 1or the coating composition of claim
 3. 6. A method for making a coatedarticle comprising the steps of: selecting a substrate; selecting thecoating composition of claim 3; applying said coating composition to atleast one surface of said substrate; removing at least a portion of thewater from said the coating composition; thereby forming one or morecoating layers associated with said substrate; and thereby forming saidcoated substrate into a coated article.
 7. A method for making a coatedarticle comprising the steps of: selecting a substrate; forming saidsubstrate into article; selecting the coating composition of claim 3applying said the coating composition to at least one surface of saidarticle; removing at least a portion of the water from said the coatingcomposition; thereby forming one or more coating layers associated withat least one surface of said article; and thereby forming said coatedarticle.
 8. Any one of the preceding claims, wherein said firstpolyester has a glass transition temperature (T_(g)) of at least 30° C.9. Any one of the preceding claims, wherein said substrate is apre-coated substrate.
 10. A can or coil coating composition comprisingthe coating composition of claim 3, in which the dispersion has a volumeaverage particle size of less than 5 microns, and wherein the dispersioncontains a first polyester, wherein said first polyester is a linear,saturated, aromatic polyester having a glass transition temperature(T_(g)) in the range of from greater than 50° C., an OH number of >3 mgKOH/g, and an acid number of less than 5 mg KOH/g, and molecular weight(M_(w)) of greater than 5,000, and an stabilizing agent comprising asecond polyester, wherein said stabilizing agent comprising a secondpolyester is compatible with the first polyester, and has an acid numberof >20 mg KOH/g.